Production of azo dyestuffs and color lakes thereof



Patented Mar. 1, 1932 UNITED STATES PATENT oi-"FrcE CARL IMMERHEISER,

or LEHNITZ, NEAR oRANIENBUnG,

AND- BODO ZSCHIMMEB,

MARTIN FRITSCH, AND HANNS FLEISCHMANN, OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., 01'' NEW YORK, N. Y

A CORPORATION OF DELAWARE PRODUCTION OF AZO DYESTUFFS AND COLOR LAKES THEREOF Ho Drawing. Application filed March 20, 1930, Serial No. 437,594, and in Germany Ju1y'28, 1925.

The present invention relates to the production of azo dyetufi's and color lakes thereof in a particularly fine dispersion.

This application is a continuation in part of our copending application Serial N 0. 103,967, filed Apr1l22, 1926.

We have found that azo dyestuffs and lakes thereof, which hereinafter are referred to as azo coloring matters, are obtained in a state of particularly fine distribution by eifecting the production of said azo coloring matters in the presence of an inert aromatic sulphomc acid, in which at least one hydrogen atom in the nucleus is substituted by a hydrocarbon side chain. The said aromatic sulphonic acids do not interfere-with the production of the azo coloring matters, which is carried out by the usual methods. The said aromatic sulphonic acids are preferably added to one of the dissolved components to which-the other reacting component is then added. For example, in the production of azo dyestufls, the aromatic'sulphonic acid is added to a solution of the coupling component, the solution of the vdiazocompound then bein added, or the aromatic sulphonic acid is ad ed to asolution of an azo lake of which is then precipitated by the addition of an alkaline earth metal salt. By

the addition of the said aromatic sulphonic acids the azo coloring matters are obtained in a state of extremely fine dispersion and therefore possess a high coloring power.

Among the aromatic sulphonic acids,

- which' may be usedeither as free acids or in the form of their salts,

those'contain'ing a hyd roc'arbon side chain of'at least two carbon atomsiare particularly suitable. The side chains may be open, for example ethyl, propyl, butyl, or other radicals, or rings as for instance in the sulphonic acids substituted by ,cyclohexyl and similar radicals, or they may link together two hydrocarbon residues; the sulphomc acids may contain one or severalsuch side chains. The presence of alky lated amino groups as substituents also proves 'to be very eflicient. We -mention as examples of compounds especially suitable for the saidv purposes: propyland butyl derivatives of naphthalene sulphonic acids;

dyestufl, the color also dimethyl metanilic acid, diamyl-alphanaphthylamine sulphonic acid and similar compounds, or their salts. Condensation products of sulphonated phenols or. naphthalene and formaldehyde may also be used. The efiiciency of the said aromatic sulphonic acids is further increased when em loying them in conjunction with Turkey red oil or similar sulphonated oils.

The following examples will further illustrate how our invention may be carriedout in practice, but the invention is not limitedto these examples. The parts are by weight.

, Ewample 1 15 parts of beta-naphthol are dissolved in 500 parts of water with an addition of 13 parts of caustic soda lye of 40 B. and 10 parts of soda ash. 10 partsof iso-propylated naphthalene sulphonic acid sodium salt dissolved in. parts of water are added to this solution and-a solution of the diazo compound prepared in the usual manner from 13.3 parts of p-nitraniline is then caused to run in. The coloring matter separates in a much finer state of division than when obtained in the absence of a sulphonic acid salt or in the presence of Turkey red oil.

Example 2 water then being run in whereby aluminium hydroxide .is precipitated. A solution of 5 parts of the sodium salt of diisopropylnaphthalene sulphonic acid in 50 parts of water, and then 79) dissolved in 40 parts of Water, are added to the said substratum, the color lake being then precipitatedby the addition of 16 parts of crystalline barium chloride in 160 parts of water. V The color lake thus produced is worked up as usual. Wall paper is stained by the said color lake purer and more vivid shades than by the same color lake produced in the absence of the sodium saltof diisopropylnaphthalene sulphonicacid.

4 parts'of Ponceau RR (see Colour Index No.

in least one hydro In the appended claims the sulphonic acids and their salts which are added according to the present invention are referred to as being inert, which is to meanthat they do not chemically take part in the reaction by interaction with the diazonium compounds or with the couplin components or with the chemicals serving or "the precipitation of color lakes. As 1s well known naphthalene sulphonic acids are capable of coupling with diazonium compounds onl when they contain at least one hlgdroxy or amino group (see for example J. van der Kam, Die Naphtalinderivate, ublished in 1927 at The Ha ue, vol. 1, page lVIII), and such naphtha ene sulphonic acids capable of coupling with diazonium compounds are accordingly not included within the scope of the present invention.. a

What we claim is 1. In the production of azo coloring matters the step, which comprises producing an azo colorin an matter in the presence 0 inert napht alene sulphonic acid, in which at least one hydrogen atom in the nucleus is substituted by a hydrocarbon side chain;

2. In the production of azo coloringmatters the step, which comprises adding an inert naphthalene sulphonic acid, in which at least one hydrogen atom. in the nucleus is substitutedby a hydrocarbon side chain, to

at least one of the dissolved components reacting with each other to form an azo coloring matter.

3. In the production of color lakes oi azo dyestuffs the step, which comprises reducing a color lake of an azo dyestufl in t e presence of an inert naphthalene 'sulphonic acid, in which at least one hydrogen atom in the nucleus is substituted by a hydrocarbon side chain. 4 p

4. In the producti n of azo 'coloring matters the step, whiclfmomprises' adding an inert naphthalene sulphonic acid, in which at least one hydrogen atom in the nucleus is substituted by a hydrocarbon dissolved azo dyestufi and producing the color lake by a metal ca able azo dyestu 5. In the .production of azo coloring matters the step, which comprises producing an azo coloring matter in the presence 0 an inert naphthalene sulphonic acid, in which at n atom is substituted by a chain containing at least of forming a lake with the hydrocarbon si 0 two carbon atoms.

. In testimony whereof we have hereunto set our hands.

' CARL IMMERHEISER.

BODO ZSCHIMMER. MARTIN FRITSCH. HANNS-FLEIS used side chain, to the the addition of a compound of. 

